Optimization of the Synthesis of Poly(octadecyl acrylate) by Atom Transfer Radical Polymerization and the Preparation of All Comblike Amphiphilic Diblock Copolymers G. STREET, 1 D. ILLSLEY, 2 S. J. HOLDER 1 1 Functional Materials Group, School of Physical Sciences, University of Kent, Canterbury, Kent CT2 7NH, United Kingdom 2 Sun Chemical, Cray Avenue, St. Mary Cray, Kent BR5 3PP, United Kingdom Received 12 July 2004; accepted 4 October 2004 DOI: 10.1002/pola.20582 Published online in Wiley InterScience (www.interscience.wiley.com). ABSTRACT: The atom transfer radical polymerization of octadecyl acrylate (ODA) has been investigated and optimized to produce polymers with predetermined molecular weights and narrow polydispersities (1.2). The poor solubility of the catalytic system formed with conventional ligands such as the N-(n-propyl)-2-pyridylmethanimine and 2,2'-bipyridine with Cu(I)Br in nonpolar reaction conditions gave poor control over molecular weight characteristics in ODA polymerizations. The use of N-(n-octyl)-2- pyridylmethanimine in combination with Cu(I)Br yielded a more soluble catalyst that improved control over the polymerization. The products from the polymerizations were further improved when an initiator, octadecyl 2-bromo-2-methyl-propanoate, similar in structure to the monomer, was used. Together, these modifications produced polymer- izations that showed true controlled character as well as products with predetermined molecular weights and narrow polydispersities. Diblock copolymers of PODA were prepared with methyl methacrylate (MMA) and olig(oethylene glycol) methyl ether methacrylate (OEGMA). The PODA-block-POEGMA copolymers are the first examples of all comblike amphiphilic block copolymers. One of PODA-block-POEGMA copolymer samples has been shown to self-assemble as micelles in a dilute aqueous solution. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1129 –1143, 2005 Keywords: octadecyl acrylate; oligo(ethylene glycol) methacrylate (OEGMA); atom transfer polymerization (ATRP); comblike polymers; block copolymers; amphiphiles; micelles; electron microscopy INTRODUCTION There is increasing academic and industrial in- terest in the use of controlled radical polymeriza- tion (CRP) processes to develop high performance products. In particular, for the coatings industry, EFKA have recently launched two acrylic block copolymer dispersants, EFKA-4300 and EFKA- 4330, synthesized with such techniques. 1 Another area where CRP may have an impact on coatings is in producing polymers that can modify surface properties. 2,3 For example, hydrophobic coatings are desirable for improving the water resistance of printed articles. Therefore, octadecyl acrylate (ODA) is of interest as a component in coatings applications, possessing highly hydrophobic crys- tallizable side chains. It also offers interest as a component of smart paints because the crystalli- zation is temperature switchable, with a transi- Correspondence to: S. J. Holder (E-mail: s.j.holder@kent. ac.uk) Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 43, 1129 –1143 (2005) © 2005 Wiley Periodicals, Inc. 1129